Secondary ethers of polyhydeic



Patented Apr; 16, 19%0 UNITED STATES 2,197,467 SECONDARY mums or romnrnaio ALCOHOLS- Theodore W. Evans, Berkeley, and Edwin Bullard, Oakland, Calif., assignors to Shell Development Company, San Francisco, Calif., a

PATENT OFFICE v corporation or Delaware I No Drawing. Original application December 12,

1936, Serial No. 115,636.

Divided and this application February 11, 1938, Serial No. 190,028

8 Claims.

This inventionrelates to new chemical compounds and more particularly to new aliphatic trihydrlc alcohol ethers characterized by the substitution of an alkoxy group of an aliphatic-secondary alcohol for at least one ofthe hydroxy groups of the trlhydric alcohol.

An object ofthe invention is to provide a novel Secondary ethers of polyhydric alcohols of the class consisting of aliphatic trihydric alcohols, one hydroxy' group of which has been substituted by the alkoiw group of an aliphatic secondary alcohol; alcohol trihydric alcohols, two hydroxy groups of which have been substituted by the alkoxy groups of aliphatic secondary alcohols, at least one of said alkoxy groups containing at least four carbon atoms; and aliphatic 25 trihydric alcohols, each hydroxy group of which has been substituted bythe alkoxy group of an aliphatic secondary alcohol, have been prepared and described for the first time. I

a The invention is described with particular ref- 30 erence to the secondary ether of the glycerols, the

term "glyceroP embracing, in addition to glycerol,

erols, which are mbraced within the scope of V 35 the invention, inc ude, among others, the following: alpha isophopyl ether of glycerol, beta isopropyl ether of glycerol, alpha secondary butyl ether of glycerol, beta secondary butyl ether of glycerol, alpha secondary amyl ether of glycerol, 40 beta secondary amyl ether of glycerol, the secondary hexyl ethers of glycerol, the secondary heptyl ethers ofglycerol and the like and their homologues analogues and suitable substitution .products; alpha isopropyl ether of beta-methyl 45 glycerol, beta isopropyl ether of beta-methyl glyc-v erol, alpha secondary butyl ether of beta-methyl glycerol, beta secondary butyl ether of betamethyl glycerol, alpha secondary amyl ether of beta-methyl glycerol, the secondary hexyl ethers 50 of beta-methyl glycerol, the secondary heptyl ethers of beta-methyl glycerol and the like and 1 their homologues, analogues and suitable substitution products; the isopropyl, secondary butyl,

I secondary amyl, secondaryhexyl, secondary hep-' 55 tyl and the like monoethers of the beta-ethyl-,'

Secondary mono-ethers of glycbeta-propyl beta-hexyland the like glycerols; the isopropyl, secondary butyl, secondary amyl, secondary hexyl, secondary heptyl and the like monoethers ofthe alpha-methyl, alpha-ethylalpha-propyl and the like glycerols,, as well as.

nassum JUL is an the secondary monoethers of the alpha alpha substituted glycerols as alpha methyl, alphaethyl glycerol, alpha beta substituted glycerols as alpha methyLbeta-methyl glycerol and the like.

It is seen that, in the above described novel 7 compounds, onehydroxy group 01' the trihydricalcohol has been replaced by the alkoxy group of an aliphatic secondary alcohol 'as isopropyl alcohol, secondary butyl alcohol, secondary'amyl alcohol, etc. One or both of the other hydroxy groups may be substituted by the alkoxy, aralkoxy or aryloxy groups of primary or tertiary alcohols or of phenolic compounds, or by the negative radicals 6f aliphatic carboxylic acids, such as in alpha-methyl, alpha secondary butyl diether of glycerol, allyl, secondary butyl diether of glycerol and phenyl, secondary butyl diether of glycerol.

Disecondary dlethers of glycerols, which are within the scope of the invention, include, among others, the following: alpha isopropyl, alpha" butyl diether of glycerol, alpha secondary butyl, beta isopropyl diether of glycerol, alpha, alpha diisopropyl diether of beta-methyl glycerol, alpha, alpha disecondary butyl diether of beta-methyl glycerol, alpha, beta diisopropyl dietheror betamethyl glycerol, the symmetrical and mixed disecondary diethers oi the beta-'ethyl-, betapropyl-betabutyl andthelike glycerols, the symmetrical and mixed disecondary diethers of the alpha substituted glycerols, and the like and their homologues, analogues and suitable substitution products. The remaining hydroxy group of the above-listed disecondary dlethers of glycerols may be substituted by the alkoxy, aralkoxy or aryloxy group of a primary or tertiary alcohol or of a phenolic compound, or it may be substituted by the negative radical of an organic carboxylic acid.

Trisecondary triethersof glycerols, which are within the scope-of the invention, include, among others, the following: trlisopropyl triether of glycerol, trisecondary butyl triether \of glycerol,

trisecondary amyl triether of glycerol, trisecondary hexyl triether of glycerol, alpha, alpha" ,diisopropyl, beta secondary butyl .triethe'r of glycerol, alpha, beta diisopropyl, alpha"se condary butyl triether of glycerol, alpha, alpha 'diisopropyl beta secondary amyl triether' of glycerol, alpha, alpha disecondary butyl, beta isopropyl triether of glycerol, and the like trisecondary tnethers of the glycerols as beta-methyl glycerol,

beta-ethyl glycerol, beta-propyl glycerol; alphamethyl glycerol, alpha, alpha dimethyl glycerol, etc., wherein the hydroxy groups are substituted by the same or different alkyl radicals of aliphatic secondary alcohols. l

A particularly useful and readily prepared group of secondary ethers of polyhydric alcohols comprises the secondary monoethers, the disec ondary diethers wherein one of the secondary alcohol radicals contains at least four carbon atoms, and the trisecondary triethers of glycerol. The secondary monoethers of glycerol may be represented by the formulae:

and HOCH2CHOR/-CH2OH, wherein R repre sents the allryl radical of an aliphatic secondary alcohol. v

The disecondary diethers of glycerol with which we are principally concerned may be represented by the formulae:

WHz-CHOH-CHa-O-R, HOCH2CHOR-CH2OR' and HO-CHz-CHOE-CHzOR, wherein R. and R are the same or diflerent secondary aikyl radicals, R representing the alkyl radical of an. aliphatic secondary alcohol, and R representing.

thealkyl radical of an aliphatic. secondary alcohol containing at least four carbonatoms to the molecule. L

The trisecondary triethers of glycerol may be represented by the formula wherein R, R, and R may be the same or different and represent allryl radicals of aliphatic secondary alcohols. 1

In our U. S Patent No. 2,067,385, which issued January 12, 1937, with which the parent application of which this application is a divisionwas copending'and a continuation-in-part thereofiwe have described and claimed a process for the.

preparation of secondary 'polyhydri c alcohol ethers, which process. comprises reacting a secondary-base oleiine, as propylene, secondary butylene, secondary amylene, etc., with an aliphatic polyhydricalcohol in the presence of a condensing agent, preferably an acid-acting con- 'densing agent, which promotes a condensing action between the olefine and the alcohol. This process is suitable for the production of some of the secondary ethers of trihydric alcohols herein described. We have, in addition, discovered that there are other methods of preparing such secondary ethers of trihydric alcohols.

One of such other methods comprises reacting a halohydrin of the trihydric alcohol to be etherified with an alkali metal salt of the desired aliphatic secondary alcohol. For example, if it is desired toprepare the alpha isopropyl ether of glycerol, dichlorhydrin may be reacted with the isopropyl alcoholate of sodium to yield the isopropyl ether of glycidol whichr'an be readily hydrated to the desired alpha isopropyl monoether of glycerol. This manner of preparing the secondaryethers of 'trihydric alcohols is described in. detail in'theillustrative examples.

' 'lhe'invention is illustrated but not limited by the following uamples which describe the preparation' of representative secondary ethers of trihydric alcohols. The parts are by weight.

Erample I About. 54.5 parts of sodium were dissolved in about 1000 parts ofsecondary butyl alcohol. This solution was stirred and heated at about C.,

while about 156 parts of ,dichlorhydrin were added. When all of the dichlorhydrin had been added, the stirring was continued and the mixture heated at about C. for about 1.5 hours. At the end-of this time, the mixture was cooled,

filtered to separate sodium chloride, and distilled under a subatmospheric pressure. Two reaction products were isolated.

The lower boilingv productiB. P. 52 C. at 14 of mercury) was the secondary butyl ether of glycidol of the formula o C:H;--(|}HOJCH:{H H:

CH: This novel compound has a specific gravity r) of 0.9137. It is a good nitrocellulose solvent. A

part of the secondary butyl ether of glycidol was heated with water in the presence of a mineral acid and hydrated to the novel alpha secondary butyl glycerol ether of the formula A good yield of this ether was obtained.-

The higher boiling fraction separated by vacuum distillation of the initial reacted mixture was the novel alpha, alpha disecondary butyl diether of glycerol of the formula c,n.-cno-omcno.ncm o-cno,m

v CH: B; This compound boils at a temperature of C.=under a pressure of 14 mm. of mercury, and it has a specific gravity (Q?) of 0.9125. This ether is a solvent for nitrocellulose. It is only slightly soluble in water.

Example If About 51 parts of sodium were dissolved in about 750 parts of secondary amyl alcohol. This solution was stirred and maintained at room temperature while about parts of dichlorhydrin were added slowly over a period of about one hour. After all of the dichlorhydrin had been the preparation of resins, etc.

.to recover acetylene from gaseous This application is a r 2,197,407. This novel compound'has a boiling temperatureof-W C. under a pressure of 16 mm. of mercury.

Its specific gravity is 0.9056. The glycidol ether possesses a limited water solubility and it is a good solvent for nitrocellulose. I

The secondary amyl ether of glycidol was hydrated to the corresponding alpha secondary amyl ether of glycerol by the following method:. About 40 parts of the glycidol ether, 400 parts of water and 0.15 part of sulphuric acid were mixed and the mixture stirred andheated under reflux for about five hours. I At the end of this time the reaction mixture was neutralized and distilled under a subatmospheric pressure. The alphasecondary amyl ether of glycerol (oan-cn-o-onrcnon-cmon) H was obtained in good yield. This compound boils at 102 C. under a pressure of 3, mm. and it has a specific gravity V 2) of 0.9836.

The novel secondary ethers of trihydric alcohols are for. the most part colorless, more or less viscous liquids of high boiling temperature and negligible vapor pressure at room temperature. The secondary ethers, particularly the secondary monoethers, may be used as substitutes for glycerol in a great many processes. In numerous cases they are more advantageously used than the glycerols because of their lower hydroscopicity and greater solvent powerfor certain materials. For example, the secondary ethers of trihydric alcohols comprehended by the invention are useful as ingredients of textile treatment media, as reagents in the manufacture of explosives, as perfume fixatives, as constituents of lubricating compositions, as constituents "of anti-freeze mixtures for use in the cooling systems of internal combustion engines, as heat-transferring media in indirect heat conduction systems, asreactants in The novel trlhydric alcohol ethers arepartlcularly useful as solvents. Many of them are good nitrocellulose solvents and are useful as plasticizers for cellulose ethers and esters. They may be used" as such or admixed with other substances, as extracting agents for organic substances as alkaloids, essential oils, essences and the like. They are excellent solvents for="acety-, lene, and they may be es. The glycerol ethers, particularly those'of lower molecular weight, are excellent solvents for acidic gases, particularly hydrocyanic acid. Rather. the secondary-ethers of trihydric alcohols are useful intermediates in the preparation of trihydric alcohols and trihy'dric alcohol derivatives. a division of our copending application, Serial No. 115,636, filed December 12, 1936, which was copending with application, Serial No. 722,567, filed April-26, 1934, which. issued as U. S. Patent 2,067,385 on Janus 'y 12. 1937. i

used as scrubbing agents The foregoing description has been made rather detailed for clearness of understandin only, and no unnecessary limitations should be understood therefrom, but the appended claims should be construed as broadly as possible in view of the prior art. V y

We claim as our invention: 4

1. An etherifled aliphatic trihydrlc alcohol, only two hydroxy groups of which have been substituted by the alkoxy groups of, aliphatic secondary alcohols, one of said alkoxy groups containing at least six carbon atoms. 0

2. An etherifled aliphatic trihydric alcohol, only two hydroxy groups of which have been substituted by the alkoxy groups of aliphatic secondary alcohols containing at least six carbon atoms.

8. The glycerol disecondary diether of the general formula R 7 zH| a, wherein R represents the alkyl radical of an aliphatic secondary alcohol, and R1 represents the blkyl radical of an aliphatic secondary alcohol containing at least six molecule. I

4. The glycerol disecondary diether of the general formula R-CHOH-CHOH-CHOH-Ri,

wherein R; and R1 are'the alkyl radicals of alialcohols at least one of which contains at least six carbon atoms.

phatic secondary 5. The glycerol disecondary diether of the general formula R-CHOH-CHOR1 H2OH. wherein R and R1 are the alkyl radicals of all phatic secondary alcohols at least one of which contains at least six car n atoms.

' 6. The glycerol disecondary diether of the general formula elm-on-b-cm-cnon-cnon-m disecondary diether of the carbon atoms to thephatic secondary alcohol containing at least six carbon atoms.

- 8. The glycerol general formula CHr0R HOCHC;H5 I i HnOH Ha wherein R1 represents the alkyl radical of 'an'aliphatic secondary alcohol containing at least six carbon atoms.

disecondary. diether of the 'rnnoponn w. Evans. nnwm F BULLARD. 

